?/EPA
             United States
             Environmental Protection
             Agency
             Environmental Monitoring
             Systems Laboratory
             P.O. Box 93478
             Las Vegas NV 89193-3478
EPA/600/R-92/190
September 1992
             Research and Development
Uranium in Water
Intercomparison  Study

A Statistical Evaluation of the
July 24, 1992 Data
                                              5168GR92NRD-17

-------
            Uranium in Water
           Intercomparison Study
              July 24, 1992
      Environmental Protection Agency
Environmental Monitoring Systems Laboratory
            Las Vegas, Nevada

-------
            UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
                        OFFICE OF RESEARCH AND DEVELOPMENT
               ENVIRONMENTAL MONITORING SYSTEMS LABORATORY-LAS VEGAS
                                  P.O. BOX 93478
                            LAS VEGAS, NEVADA 89193-3478
                                   (702/798-2100)
Dear Participant,

   Enclosed are the results of the Nuclear Radiation Assessment Division (EMSL-LV)
Intercomparison Study for Uranium in Water; July 24, 1992.

   Please take a few minutes to review this report and the analytical data your
laboratory submitted to us.  If there are any apparent  discrepancies, please notify
us immediately.

   We encourage you to make use of the computer-automated data-entry system that
has been in place for some time now. As the number of participants increases, and
it becomes unrealistic for us to receive results by mail or FAX, the computer system
will be our only avenue for accepting data.

   If you have any questions or comments, please send a message via the data-entry
system or contact Frank Novielli at 702/798-2159 or Patricia Honsa at 702/798-2141.
                                          Sincerely,
                                          Frank Novielli
                                          Senior Chemist
                                          Radioanalysis Branch
Enclosure

-------
                 NOTICE

This material has been funded wholly by
the U.S. Environmental Protection Agency.
It has been subject to the Agency's review,
and it has been approved for publication
as an EPA document.

-------
           EMSL-LV Intercomparison Study: Uranium in Water, 24-Jul-1992         1/7


   The following pages consist of separate sections for each of the nuclides in this study with four
parts per section. After the first, each part is separated from the next by a new page or a thick
horizontal bar.  The first page of each section is a statistical summary for the nuclide and starts
with a statement of the known value, the control limits, and the warning limits.

   The warning limits are placed at two normalized standard deviations above and below the
known value and the control limits are three normalized standard deviations above and below
the known value. If you keep control charts, these values will be useful for anticipating problems
with the accuracy of your analytical methods.
   The coin shaped pie chart at the top of the summary page shows the fate of all the samples
sent out in number and percentage terms. The pie chart starts at the top and rotates clockwise.
The first sector represents those participants who submitted analytical results within both the
warning and control limits. The next sector represents those who are in the warning region but
not out of control. The third sector represents those who are out of control, but have passed
the outlier test.  The fourth sector represents those who have failed the outlier test. The last
sector represents those participants who have failed to respond properly. This is the case if no
analytical results were returned, or less than three determinations were reported, or if the results
were received too late.  The reeding on the edge of the coin is spaced at one percent intervals, and
the sector shading becomes darker as the  data reliability decreases. Sectors with zero width are
not shown.
   The table in the center shows a number of statistical quantities calculated from the submitted
data based on the mean and median values in relation to the known value, both before and after
outlier removal. The lower pie chart uses the same construction as the upper chart and shows
the distribution of properly submitted data in terms of deviation from the known value divided
into sectors representing  one, two, three, and greater than three normalized standard deviations.

   The second part is an  alphabetical listing, in lab-code order, of submitted data and several
calculated quantities. An entry that is shaded has been rejected because of one of the reasons
listed above or failure of the outlier test. The fifth and sixth columns are a measure of laboratory
precision. The Range analysis is a normalized value that you may use to keep precision control
charts. If this value is between 2.0 and 3.0, your analytical process precision is in the warning
zone; if it exceeds 3.0 it is out of control. The eighth and ninth columns are the differences from
the mean of all non-outliers and from the  known value, respectively. A tag symbol may appear in
the last column. Each page with tags has a symbol definition summary at the bottom.  If there is
no tag symbol, the data is within the control limits, but it may be in the warning zone.

   The third part is a three-column listing of result average, tag symbol, and lab-code in average
order excluding those labs not responding properly. In this order, all outliers and out-of-control
results appear at the top  or bottom of the  list.
   The last part is two bar chart displays showing frequency distributions of responding
participants. The first chart places the known value at the center and a bar at each 0.2 unit of
expected precision. The second chart places the mean of the reported measurements at the center
and a bar at each 0.2 unit of standard deviation. In both cases,  a bar includes those results within
0.1 unit up to the maximum of six. Any results more than six units from the center value  are
shown cumulatively by a shaded bar one past the sixth unit. If the central tendency of the known
value distribution falls away from the center, an error in accuracy is indicated. If the distribution
is broad, poor precision is indicated. The  mean value distribution is similar but uses the average
and standard deviation of reported results as its basis.

-------
             EMSL-LV Intereomparison Study: Uranium in Water, 24-Jul-1992
                                    2/7
Uranium (Natural)                  Statistical Summary                      151 Participants
The known value of this nuclide is 4.0 pCi/1 with an expected precision of 3.0; the control limits
are 0.0 to 9.2; the warning regions are 0.0 to 0.5 and 7.5 to 9.2
3O(19.9 %) Failed to respond *%
1(O.7%) Outliers'
         Statistic
              , 120(79.5 %) Within all limits
Respondents
         Non-outliers
Mean
Std. Dev.
Variance
% Coef. of Var.
% deviation of mean from known value
Norm. dev. of mean from known value
Median
% deviation of median from known value
Norm. dev. of median from known value
      4.03
      0.93
      0.87
     23.10
      0.67
      0.03
      4.00
      0.00
      0.00
Grand Avg 3.97
            0.72
            0.52
           18.24
           -0.67
           -0.04
            3.98
           -0.42
           -0.02
1(O.8 %) More than 3 norm. S.D. •„,
                                 *
          ; 116(95.9 %) Within 1 norm. S.D.
                           of known value
                                                           4(3.3 %) Between 1 and 2 norm. S.D.

-------
3/7 EMSL-LV Intel-comparison Study: Uranium in Water,
Uranium (Natural)
Lab
A
AA
AE
AF
AI
AJ
AK
AL
AP
AW
AZ
BA
BB
BC
BG
BG
BH
BK
BL
BM
BN
BO
C
CA
CE
CG
CJ
CK
01*
CO
CS
D
DB
DE
DO
DP
DT
DZ
E
EB
MO
ER
FE
FJ
Res. 1
4.9
4.0
2.8
4.0
4.1
4.7
4.0
2.3
4.0
2.9
3.2
3.8
3.9
3.8
3.8
3.9
3.2
4.1
n
4.7
4.5
4.3
4.1
3.4
3.6
3.6
3.9
4.2

4.1
4.0
4.1
3.0
4.4
4.4
2.9
6.1
3.0
3.9
3.2
- '
4.0
3.5
2.8
Res. 2 Res. 3
4.8
4.3
2.6
4.1
4.2
4.6
3.1
1.6
4.7
3.0
3.1
4.8
3.9
3.7
3.8
4.0
2.7
4.0
-
4.7
3.7
4.2
3.7
3.7
3.6
4.0
3.9
4.8
- '
3.9
3.9
4.0
3.0
4.5
4.5
3.1
3.1
2.9
3.9
3.2
••
3.5
3.7
2.9
4.8
3.9
2.7
4.3
4.0
4.5
4.3
2.0
4.6
2.2
3.4
4.3
4.1
3.7
3.8
3.9
2.5
4.0

4.3
4.1
4.6
4.5
3.6
3.5
4.1
4.0
4.5
-
4.3
4.0
4.0
2.0
4.7
4.5
3.2
3.5
3.0
4.8
2.4
,,
4.0
3.5
2.8
• = No data submitted
0 9
Insufficient
data
X =
Exper.
Sigma
0.06
0.21
0.10
0.15
0.10
0.10
0.62
0.35
0.38
0.44
0.15
0.50
0.12
0.06
0.00
0.06
0.36
0.06

0.23
0.40
0.21
0.40
0.15
0.06
0.26
0.06
0.30
'
0.20
0.06
0.06
0.58
0.15
0.06
0.15
1.63
0.06
0.52
0.46
_,
0.29
0.12
0.06
Rnganal
24-Jul-1992

Normalized deviation
(R + SR) Average
0.020
0.079
0.039
0.059
0.039
0.039
0.236
0.138
0.138
0.158
0.059
0.197
0.039
0.020
0.000
0.020
0.138
0.020

0.079
0.158
0.079
0.158
0.059
0.020
0.098
0.020
0.118
,
0.079
0.020
0.020
0.197
0.059
0.020
0.059
0.591
0.020
0.177
0.158

0.098
0.039
0.020
4.83
4.07
2.70
4.13
4.10
4.60
3.80
1.97
4.43
2.70
3.23
4.30
3.97
3.73
3.80
3.93
2.80
4.03

4.57
4.10
4.37
4.10
3.57
3.57
3.90
3.93
4.50

4.10
3.97
4.03
2.67
4.53
4.47
3.07
4.23
2.97
4.20
2.93
'
3.83
3.57
2.83
TAG SYMBOLS
Determined
to be an outlier

(grand-avg) (known) Tag
0.50
0.05
-0.74
0.09
0.07
0.36
-0.10
-1.16
0.27
-0.74
-0.43
0.19
0.00
-0.14
-0.10
-0.02
CrO.68
0.03

0.34
0.07
0.23
0.07
-0.23
-0.23
-0.04
-0.02
0.30

0.07
0.00
0.03
-0.75
0.32
0.28
-0.52
0.15
-0.58
0.13
-0.60

-0.08
-0.23
-0.66
ft s Above
& s Below
0.48
0.04
-0.75
0.08
0.06
0.35
-0.12
-1.17
0.25
-0.75
-0.44
0.17
-0.02
-0.15
-0.12
-0.04
-0.69
0.02
*
0.33
0.06
0.21
0.06
-0.25
-0.25
-0.06
-0.04
0.29
*
0.06
-0.02
0.02
-0.77
0.31
0.27
-0.54
0.13
-0.60
0.12
-0.62
i-
-0.10
-0.25
-0.67
control limit
control limit

-------

EMSL-LV Intel-comparison Study:
Uranium (Natural)
Lab Res. 1 Res. 2 Res. 3
FN
FZ
GO
GN
GO
GQ
GZ
HE
HK
HL
HP
Htl
HY
I
H>
IE
J
JE
JG
JK
JP
JS
JU
JY
K
KH
L
LB
LH
LM
LT
LZ
ME
MN
MS
N
NA
NH
NK
JNO
NT
OA
OB
OF
• =
0 s
4.0
3.1
* ff J , ' f
5.4
,
4.8
4.4
3.6
4.0
3.8
3.8
"
3.6
3.9
6.2
4.9
4.1
5.8
4.5
3.8
3.7
3.7
2.0
4.1
3.9
3.6 	
•* f *' ff
4.0
3.1
4.2
3.9
3.4
ff ' ff
3.7
3.1
4.9
4.1
2.5
f ff ' S
3.3
4.1
3.9
3.8
3.3
-,*•' , -
5.4
f
4.7
4.1
3.6
4.0
3.8
3.9
",'', * '
3.4
4.2
6.2
4.5
4.3
6.8
3.2
3.9
3.7
3.9
2.7
4.3
3.9
3.6
f f ff ' ,
4.0
3.2
4.3
3.8
3.4

3.7
3.4
4.6
5.4
3.2
-, ,/ /
3.0
4.1
4.4
3.9
4.2
,' /
5.1
f
4.4
3.7
3.6
4.0
3.7
3.9
-,
3.1
4.3
6.2
5.1
4.3
5.2
3.9
4.0
3.7
4.2
2.6
4.3
3.8
3.7
'/* ,, ',
4.0
3.8
4.2
3.8
3.5
,
3.8
4.7
4.1
5.5
3.0
j
2.7
4.2
6.1
No data submitted
Insufficient data

x =
Exper.
Sigma
0.10
0.59
'
0.17
'
0.21
0.35
0.00
0.00
0.06
0.06
'
0.25
0.21
0.00
0.31
0.12
0.81
0.65
0.10
0.00
0.25
0.38
0.12
0.06
0.06
f f
0.00
0.38
0.06
0.06
0.06

0.06
0.85
0.40
0.78
0.36
f
0.30
0.06
1.15
Uranium in Water, 24-Jul-1992
4/7
Rng anal Normalized deviation
(R + SR) Average (grand-avg) (known) Tag
0.039
0.217
'
0.059
,
0.079
0.138
0.000
0.000
0.020
0.020
-
0.098
0.079
0.000
0.118
0.039
0.315
0.256
0.039
0.000
0.098
0.138
0.039
0.020
0.020

0.000
0.138
0.020
0.020
0.020

0.020
0.315
0.158
0.276
0.138
,, ' -
0.118
0.020
0.433
3.90
3.53
-, '", ->'
5.30
' j
4.63
4.07
3.60
4.00
3.77
3.87
/ ' ' ' ' '"/ '
3.37
4.13
6.20
4.83
4.23
5.93
,
3.87
3.90
3.70
3.93
2.43
4.23
3.87
3.63
', ' ' ''' ' "
4.00
3.37
4.23
3.83
3.43

3.73
3.73
4.53
5.00
2.90

3.00
4.13
4.80
TAG SYMBOLS
Determined
to be an
outlier
-0.04
-0.25
•' '
0.77
;
0.38
0.05
-0.22
0.02
-0.12
-0.06
•* f f
-0.35
0.09
1.29
0.50
0.15
1.13
-0.06
-0.04
-0.16
-0.02
-0.89
0.15
-0.06
-0.20

0.02
-0.35
0.15
-0.08
-0.31

-0.14
-0.14
0.32
0.59
-0.62
* f
-0.56
0.09
0.48
It s Above
li 3 Below
-0.06
-0.27
' *
0.75
.. *
0.37
0.04
-0.23
0.00
-0.13
-0.08
•
-0.37
0.08
1.27
0.48
0.13
1.12
*
-0.08
-0.06
-0.17
-0.04
-0.90
0.13
-0.08
-0.21
•*
0.00
-0.37
*
0.13
-0.10
-0.33
*
-0.15
-0.15
0.31
0.58
-0.64
•
-0.58
0.08
0.46
control limit
control limit

-------
5/7 EMSL-LV Intel-comparison Study: Uranium
in Water,
24-Jul-1992

Uranium (Natural)

Lab
OK
OM
OS
OY
OZ
P
PB
PC
PE
PI*
PP
PQ
PV
PW
PX
Pit
QM
QQ
QU
QX
QY
QZ
RC
RG
RK
RM
RN
HP
RR
RV
RW
RZ
S
sc
SD
SF
SI
SM
SO
ss
ST
SW
SZ
T

Res. 1


2.5
5.0
6.4
4.4
4.5
-


3.7
3.5
11*0

5.0

4.7
3.4
4.3
'
4.1
3.8
4.2
4.0

3.2
4.0
5.0
4.1
5.6
4.9
4.4
3.4
3.8
3.6
4.1
2.8
3.8
3.6
3.7
3.8
3.4
4.2
3.6

Res. 2
'

2.3
5.2
6.2
3.7
5.0

f

3.6
3.6
103

5.4

4.6
2.2
4.6

4.1
3.7
3.8
3.9

3.2
3.9
5.0
3.9
5.3
4.8
4.4
3.5
3.8
3.4
4.2
2.8
4.1
3.4
3.7
3.9
3.6
3.9
3.3

Res. 3
,,

2.1
4.9
6.4
4.4
5.0

%

3.7
3.7
9*5

4.8

4.7
2.6
4.8
'
4.1
4.0
4.2
4.1

3.5
3.9
6.0
3.9
5.8
4.8
4.2
3.7
3.9
3.4
4.2
2.8
4.2
3.9
3.8
4.1
3.6
4.0
3.1
• 3 No data submitted
0 =
Insufficient
data
X 3
Exper.
Sigma
"•
,
0.20
0.15
0.12
0.40
0.29
-


0.06
0.10
031

0.31

0.06
0.61
0.25

0.00
0.15
0.23
0.10
f
0.17
0.06
0.58
0.12
0.25
0.06
0.12
0.15
0.06
0.12
0.06
0.00
0.21
0.25
0.06
0.15
0.12
0.15
0.25
Rng anal
(R + SR)
-
*
0.079
0.059
0.039
0.138
0.098
'


0.020
0.039
0*205

0.118

0.020
0.236
0.098

0.000
0.059
0.079
0.039

0.059
0.020
0.197
0.039
0.098
0.020
0.039
0.059
0.020
0.039
0.020
0.000
0.079
0.098
0.020
0.059
0.039
0.059
0.098
Normalized deviation
Average


2.30
5.03
6.33
4.17
4.83



3.67
3.60
10.43

5.07

4.67
2.73
4.57

4.10
3.83
4.07
4.00

3.30
3.93
5.33
3.97
5.57
4.83
4.33
3.53
3.83
3.47
4.17
2.80
4.03
3.63
3.73
3.93
3.53
4.03
3.33
TAG SYMBOLS
Determined
to be an outlier
(grand-avg) (known) Tag

'
-0.97
0.61
1.36
0.11
0.50


'
-0.18
-0.22
&78
'
0.63

0.40
-0.72
0.34

0.07
-0.08
0.05
0.02

-0.39
-0.02
0.79
0.00
0.92
0.50
0.21
-0.25
-0.08
-0.29
0.11
-0.68
0.03
-0.20
-0.14
-0.02
-0.25
0.03
-0.37
ft 3 Above
II 3 Below
*
» ;
-0.98
0.60
1.35
0.10
0.48
« \
* :
.
-0.19
-0.23
xj 71 ^&
*
0.62
«
0.38
-0.73
0.33
»
0.06
-0.10
0.04
0.00
»
-0.40
-0.04
0.77
-0.02
0.90
0.48
0.19
-0.27
-0.10
-0.31
0.10
-0.69
0.02
-0.21
-0.15
-0.04
-0.27
0.02
-0.38
control limit
control limit

-------
EMSL-LV Intercomparison Study: Uranium
Uranium (Natural)
Lab Res. 1 Res. 2
TA 3.8 4.2
-i» ;' ' '-'* ''"';''"' -'
a»"- ' -<" ' - '"' -
TI 4.2 4.6
, T' - '-/"
TL 4.5 4.2
TQ ' ''' ' '-
TS 4.3 4.2
TU 4.8 4.7
'TV' ' , '', " ''
U 4.0 4.2
W 4.2 3.9
Y 4.0 3.8
Z 3.9 3.9

Exper. Rng anal
Res. 3 Sigma (R + SR)
4.1 0.21 0.079
, ' f * f *
' > - i *''?-' -
4.2 0.23 0.079
*,,,/'''
' ' ' , ' '
4.3 0.15 0.059
ff j / '
4.3 0.06 0.020
4.5 0.15 0.059
' ,
4.5 0.25 0.098
3.9 0.17 0.059
3.9 0.10 0.039
4.2 0.17 0059
in Water, 24-Jul-1992

Normalized deviation
Average (grand-avg) (known)
4.03 0.03 0.92
'- '-'- '-'"'*' " 'X>' '<-. - ':',-
' ff ' ' f / sf ' *' , '
4.33 0.21 0.19
' ; ' '''',,'''* v
''',','''' ;, •'•',,
4.33 0.21 0.19
' , '' ' ' f
4.27 0.17 0.15
4.67 0.40 0.38
,
4.23 0.15 0.13
4.00 0.02 0.00
3.90 -0.04 -0.06
4.00 0.02 0.00
6/7
'
Tag
, ,,
' m ' '
,*
_.
*
* ,

*


* ,




Data sorted by Laboratory Average
Average Tag
1.97
2.30
2.43
2.67
2.70
2.70
2.73
2.80
2.80
2.83
2.90
2.93
2.97
3.00
3.07
3.23
3.30
3.33
3.37
3.37
3.43
3.47
3.53
3.53
3.53
3.57
• = No data submitted
0 = Insufficient data
Lab Average Tag
AL 3.57
OS 3.57
JY 3.60
DB 3.60
AW 3.63
AE 3.63
QQ 3.67
SI 3.70
BH 3.73
FJ 3.73
NK 3.73
EB 3.73
DZ 3.77
NT 3.80
DP 3.80
AZ 3.83
RM 3.83
T 3.83
LM 3.83
HY 3.87
ME 3.87
SD 3.87
FZ 3.90
SW 3.90
S 3.90
FE 3.90
TAG SYMBOLS
Lab Average Tag
CE 3.93
CA 3.93
PQ 3.93
HE 3.93
L 3.93
SO 3.97
PP 3.97
JS , 3.97
SS 4.00
N 4.00
MS 4.00
BC 4.00
HL 4.00
BG 4.03
AK 4.03
SC 4.03
QZ 4.03
LZ 4.03
ER 4.07
KH 4.07
JK 4.07
HP 4.10
Y 4.10
JP 4.10
FN 4.10
CG 4.10
11 = Above control
x = Determined to be an outlier & s Below control
Lab
ST
RN
JU
CJ
BG
RR
CS
BB
Z
W
RG
LH
HK
TA
SZ
SM
D
BK
RC
GZ
AA
QY
CO
C
BN
AI
limit
limit

-------
7/7 EMSL-LV Intercomparison Study:
Uranium in Water, 24-Jul-1992
Uranium (Natural)
Data sorted by Laboratory Average
Average Tag Lab Average Tag Lab Average Tag . Lab
4.13 OB
4.13 I
4.13 AF
4.17 SF
4.17 P
4.20 E
4.23 U
4.23 LT
4.23 DT
4.23 K
4.23 J
4.27 TS
4.30 BA
4.33 TL
4.33
4.33
4.37
4.43
4.47
4.50
4.53
4.53
4.57
4.57
4.60
4.63
4.67
4.67
TI
RZ
BO
AP
DO
CK
NA
DE
BM
QU
AJ
GQ
TU
QM
4.80 OF
4.83 RW
4.83 PB
4.83 IE
4.83 A
5.00 NH
5.03 OY
5.07 PX
5.30 GN
5.33 RP
5.57 RV
5.93 JE
6.20 ID
6.33 OZ
10.43 x PV
% Frequency distribution of responding labs( expected prec. vs known value)

.

on, _ ____ __________




10

•J
-.•In






.._._
exP' prec- kn wn
value
% Frequency distribution of responding lah« std dev.

30


|


~6 '4 std. dev.
• s= No data submitted
0 s Insufficient data
• i
-.•In



• • l l
exp. prec. +4 +6
vs mean value)

	
H
-2 *2
mean
value
TAG SYMBOLS
x s Determined to be an outlier





—
std. dev. +4 +6

ft s Above control limit
•U = Below control limit I

-------